Method of making high viscosity index lubricating oils



June 1, 1937. E. w. GARDINER E-r AL 2,082,204

I METHOD OF vMAKING HIGH VISCOSITY INDEX LUBRICATING OILS original FiledJune 11', 1934 O ,JoH/v w GREENE ARTHUR L. LVM/4N Patented June l, 1937.

UNITED STATES PATENT oFFlcE METHOD F MAKING HIGH VISCOSITY INDEXLUBRICATING OILS Elmslie W. Gardiner, Berkeley, John W. Greene,

Richmond, and Arthur L. Lyman, Berkeley,V Calif., assignors to StandardOil Company of California, San Francisco, Calif., a corporation ofDelaware' Original application June 11, 1934, Serial No. 730.064.Divided and this application March 11., 1935, Serial No. 10,478

11 Claims.

This invention relates to hydrocarbon lubricating oils which haveextremely :dat viscosity-temperature curves,-that` is, whose viscosityindices (as defined, for example, by Dean and Davis in Chemical andMetallurgical Engineering,

l1929, vol. 36, page 618) are extremely high. 'I'he invention alsorelates to processes for producing hydrocarbon lubricating oils whichpossess this desired property.

This application is a division of our co-pendlng application Serial No.730,064, iiled June 11, 1934, which .related more particularly totheproduction of high viscosity index 'oils of substantially'the samemolecular weight range as `that of the initial hydrocarbons from whichthey are prepared; the present divisional application relates mostparticularly to the production of high viscosity index oils ofsubstantially higher molecular weight range than that ofthe hydro- Yably'higher viscosity indices than those of the most superior naturallyoccurring oils, and to provide suitable methods of producing them. It isanother purpose of the invention to provide lubricating oils of suchhigh viscosity indices that very considerable amounts of low viscosityindex oils may be blended or mixed therewith without lowering theviscosity index of the blendor mix l below those of the most superiornaturallyoccur- Aring oils.

We have found that the viscosity indexof the hydrocarbons or series ofhydrocarbons in the lubricating oil range of boiling points increases asthe structure of the hydrocarbon molecules dices far higher than thoseof the most superior parailine base lubricating oils known.

It is a purpose of the invention to provide hydrocarbon lubricating oilswhose molecular structure approaches that of the normal straight chainparaiiines and whose viscosity indices approach those of the normalstraight chain parafnes themselves, but whose uidity is retained torelatively low temperatures and whose Viscosity and boiling points maybe of any desired range.

The oils of our invention are produced, generally, by dehydrogenatingessentially saturated hydrocarbons of the normal straight chain series,

for example, the parafline waxes, to form olenes and dioleflnes, and,if-desirable, polymerizing the produced olenes and dioleflnes, wholly orin part, to form higher average molecular weight hydrocarbons of anydesiredvolatility or viscosity range. 'I'he dehydrogenated parailines(oleiines and diolenes) have the same molecular structure, so far aslength of chain is concerned, as the saturated hydrocarbons from whichthey are obtained, and moreover, the product-is liquid at ordinarytemperatures. wholly or in part, branched chains may b e introduced,but, due to the length of chain in the hydrocarbons polymerized, allsuch branched v'chains in the product are of great length, however farpolymerization may be allowed to progress. The produced oils are liquidrelatively low temperatures, and possess extremely high viscosityindices, as is exemplified below.

Dehydrogenation of the saturated straight chain hydrocarbons maysuitably bebrought about by chlorination, followed-by dechlorination andthe evolution of hydrochloric acid, the latter step taking place in thepresence of a dechlorination catalyst which may also be apolymerizationL catalyst, if products of high viscosity are desired.

Although the process as described below is exemplied by the use ofparamne waxes as saturated straight chain hydrocarbons, it will beapparent that the benets of the invention may be obtained by the use ofother hydrocarbon materials, and that the more nearly the originalsaturated material approaches the single, normal straight chain inmolecular structure the greater will be the benefits obtained in thepractice of the process.

In the practice of the process:

-Paramne wax (for example, crude scale wax, match wax, Parawax, etc.)`is chlorinated by direct contact with'chlorine at temperatures of 130 to210 F. or slightly above. Between these Upon polymerization,

temperatures the rapidity and degree of chlorination of the waxincreases with increasing temperature; at temperatures of 250 F. orhigher, however, decomposition of part of the chlorparaffines takesplace, and hence are to be avoided. chlorination catalysts, such astraces of iodine,v may be used, but are generally not necessary. Emcientcontacting of gas and liquid obviously vincreases the rate ofchlorination.

In the chlorination step, chlorination of all of the parafllnehydrocarbons in one operation is impractical, and even undesirable. Thusit has been found that as the degree of chlorination increases, theproportions of diand tri-chlor parafnes increase, with respect tomonochlorl paraines; moreover, as the proportions of diand higher chl'orderivatives increase, the viscosity oi' the dechlorinated productincreases, probably by reason of the greater ease of polymerization ofthe di-, tri, etc., oleflnes produced.

Further than this, the viscosity index of the dechlorinated product,whether polymerized to a high or low degree is lower by reason of theformation of di-, tri, etc., chlorparaflines, for, as stated above, thelength of chain of the dehydrogenatedhydrocarbons has been found todetermine in large part the viscosity index of the oil,

and it is apparent that the dechlorination of monochlorparamnes willproduce hydrocarbons with the longest and most nearly normal straight nchains. f

The eiect of increasing degree of chlorination upon the relativeproportions of mono, diand vtri-chlorparailines is brought out in thetable From a consideration of these data it is apparent that 4when aproduct of low viscosity. or a product of high viscosity index (whetherof low or high viscosity) is desired, the degree of chlorination shouldnot be high, in any single chlorinating operation. Low degree ofchlorination may be combined with convenience and high mciency of waxutilization b'y chlorinating for a brief period, say to a point when3-6% by weight of chlorine has been absorbed, on the basis of waxltreated, and cooling the partially chlorinated mixture tov70 F. orbelow. The chlorparamnes, whatever their.

degree of. chlorination, are light mobile liquids at very lowtemperatures, whereas, as is well known, the paraihne waxes are solidbelow about 110 F. It has been found that the chlorinated Vparaflinesare excellent crystallizing agents for the unchlorinated waxes, and thatthe' waxes are essentially insoluble in them. By cooling thechlorination mixture to` '70 F. or below, very good 1 separation ofchlorinated and unchlorinated hydrocarbons may be effected by the use ofa bull: centrifuge without the use o f a lter aid, as is invariablynecessary in the removal of solid waxes from crude petroleum distillatesor residue. In this manner unchlorinated wax, inert;y in the remainingsteps in the process, is prevented from becoming an ingredient of thenal oily product ;v

, moreover; by return of the wax to the chlorinating step in theprocess, its utilization is made substantially complete.

For the several reasons advanced above, we prefer that chlorparaillnesbe produced containing from 1323% chlorine, on a wax-free basis, 5 andthat unchlorinated wax be removed by simple bulk centrifugation andreturned for use in a subsequent chlorinating operation. Hereinafter,the terms chlorinated paraiilnes" and chlorparafilnes are to beinterpreted on a waxl0 free basis, that is, after removal ofunchlorinated wax.

In effecting chlorination of this type of hydrocarbons, the use of ironreaction vessels, or of ferrous alloy vessels in general, has been foundto l5 produce inferior products, especially as concerns the color of theilnished dechlorinated oils. Lead or porcelain lined vessels, ttings,etc., are found to have no deleterious effect of this character, f andhence are preferred in the construction of 20 the chlorinatingapparatus.

'I'he wax-free chlorparafdnes are dechlorinated at elevated temperatureswith the aid of a dechlorinating catalyst. Hydrochloric acid is evolved,and oleflnes, dioleiines, etc., depending 25 upon the degree ofchlorination (as brought out above), are produced. In -the absence ofpolymerization these hydrocarbonsy have the same molecular structure asthat of the original wax, namely, 'single normal straight chains.Whether 30 polymerization is or is not allowed to take place; theproduced dechlorinated hydrocarbons are entirely of the unsaturatedseries,-oleflnes, diolefines, etc., and/or their polymers. v

4'I'he dechlorination catalyst may also be a poly- 35 merizationcatalyst, if products of high viscosity are desired, and there are givenhereinbelow examples descriptive of the use of both non-polymerizing andpolymerizing dechlorination catalysts. 'Iypical of the first class ofcatalyst (de- 40 chlorinating, non-polymerizing) are various of theadsorbent earths,-clays of both the fullers earth and bentonitetypes-and silica gel. Typical oi' the second class of catalyst(dechlorinating,

polymerizingl are metallic :aluminum and alu- 45 minumamalgam. Anhydrousaluminum chloride occupies a position intermediate between these twotypes, so far as polymerization is concerned:

When using the clay or adsorbent earth 'type 50 of catalyst, thechlorparaiiines'and clay are heatmoval the mixture is allowed to coolsomewhat and the clay separated by filtration. 'I'he result- 60 ing oilsare very light in color and possess a green bloom or fluorescence; theyarey relatively low in viscosity.

, The figure exempliiles the lines of ilow of a system well adapted tocarry out the processes 65 of the invention. In the gure:

"I'he vwaxy hydrocarbon feed stockfenters wax feed tank P through line Iand is there held above the melting point of the wax but not above about250 F. Thence it flows through line 3 to chlorin- 70 ator A, in whichpartial chlorination takes place. Liquid chlorine from storage vessel Npasses through line 6 and vsuitable pressure reducing and regulatingvalves (not shown) to vaporizer D,

thence through line 1 and into chlorinating ves- 75 aosaaos sel A, whereit is allowed to bubble up from a suitable distributor through the waxhydrocarbons. Unabsorbed chlorine passes from the chlo rinator A throughline and may be recovered by absorption in a solvent therefor, as in thevessel M, as shown.

Upon the formation of chlorparamnes desired extent, the reaction mixtureis pumped to chlorinated wax storage Q, whence it passes through line ilto chiller B for the crystallization of unchlorinated waxes and thus,through line 8:. to bulk centrifuge C. Liquid chlorparamnes pass tostorage vessel R, as shown, and unchlo'rinated waxesare returned to waxfeed tank P, diagrammatically represented as through the line 2.

From vessel R the chlorparamnes are pumpedv through heater E anddechlorinating vessel D, either by-passing the catalyst chamber S, inthe line lll, or passing therethrough as shown. vCirculation into andout of the heater E maintains the temperature at the desired point', anddisposition of the dechlorinating, polymerizing type of catalyst invessel S and of the de'chlorinating, non-polymerizing type of catalystinthe vessel D, fed as desired through the entry l l, suitably in theform of a slurry in oil, allows the simultaneous use of both types ofcatalyst, or ofveither, alone,

solvent as that employed in the absorption of the y chlorine passed fromthe chlorinator A. p

Upon complete dechlorination, the entirely oleflnic, largely mono-olenicoil, of extremely high viscosity index and of viscosity regulable inac;-

cordance with the invention, may be cooled as by passage through thecooler U, and all traces.l

Example 1.-A yellow crude scale Wax was` chlorinated to a chlorinecontent of 18.6% by weight, on a wax-free basis, and the chlorparaffinesseparated from unchlorinated wax by bulk centrifuging at 35 F. The fluidchlorparanes were mixed with 10% by weight of 30-60 mesh Florida clay,such as is useclfor decolorizing pe# troleum lubricating oils, and themixture heated, with agitation, to 500 F. during a period of about 2hours'; the temperature of the mixture was held at 500 F. for 2 hours,by which time HC1 evolution had ceased. The dechlorinated mixture wascooled and filtered free from clay. There was no oil-insoluble sludgeformed, nor did there ppear to be any loss of hydrocarbon materialexcept that held up on the clay. A red oil with a green bloom. havingthe following characteristics, was obtained:

Viscosity at F 173 Secs. Saybolt Universal Viscosity at 210 F-- 48 Secs.Saybolt Universal Viscosity index (Dean 8i Davis) 137 Pour 50 F. Solid45F.

Example 2.-A chlorinated parailine, dewaxed and containing 18.6%chlorine by weight, on a wax-free basis, made b y the chlorination ofyellow crude scale wax, was mixed with 10% by weight of an acid-treated200 mesh decolorizing clay of the montmorillonite type and heated to 525F. as rapidly las HC1 evolution permitted;

lto the y were as follows:

Viscosity at 100 F 144 Secs. Saybolt -Universal Viscosity at 210 F-- 44Secs. Saybolt Universal Viscosity index---" 122 Pour 60 F. Solid 55 F.

This oil was dewaxed using four volumes of liqueed butane to one volumeof oil, at 40 F. The dewaxed oil had the following characteristics: i

Viscosity at 10.0 F-- 151 Secs. Saybolt Universal Viscosity at 210 F--44 Secs. Saybolt Universal Viscosity index 113 Pour 0-F. Solid 5 F.

creases rapidly with temperature rise. The reaction is'continued untilHC1 evolution is complete,

after which the catalystis separated and the oil v clarified, as before.By reason of the considerable increase in viscosity attending the use ofthis type of catalyst, an inert .diluent, such as Apurifled (inert)kerosene, may in extreme cases be desirable as a diluent to .facilitatehandling; theA diluent may later be removed, as by ordinary or steamdistillation. The resulting oils are darker in color than those preparedwith the clay type dechlorinating catalysts; they are of relatively highviscosity, by reason of the polymerization taking place simultaneouslywith dechlorination.

Example 4.-Substantially wax-free chlorparamnes containing 21,7%chlorine by weight, made from yellow crude scale wax, was heated withv0.5% by weight o f aluminum amalgam, with,

agitation. Evolution of HC1 Vbegan at about 200 F. lThetemperature wasraised vto about 300 F. as rapidly, as HC1 evolution would permit, andhem at 300 F. for about 3 hours, by which time deohlorination wascomplete. No sludge, such as is characteristic of the use of anhydrousaluminum chloride, was formed with the use of.

the aluminum amalgam. The oil was filtered free from aluminum hydroxide,after steaming to remove traces of hydrochloric acid The resulting oilhad the following characteristics:

Viscosity at 100 F-- 690 Secs. Saybolt Universal Viscosity at 210 F-- 88Secs. Saybolt Universal Viscosity index 137 Pour 65 F. Solid 60 F.

mercury, by weight; it is washed free of .hy--

droxide by means of alcohol, and, because'of its great reactivity, isadded immediately to the chlorparaiiine in the reaction vessel. f

Example 5.--Wax-free chlorparaillnes containing `18.6% chlorine cwereheated with 0.5% by weight of clean aluminum turnings. As thetemperature rose, dry AHC1 gas was bubbled in small amount through theliquid. At about 200 F. dechlorination commenced, and the introductionof dry HC1 was thereupon discontinued. The temperature was increased to300 F. and held at that point for about 2 hours, by which timedechlorination was complete. As was noted above, with the use ofaluminum amalgam, no sludge was formed with the use of metallic aluminumas catalyst. The resulting oil, after separation from the aluminumcatalyst and steaming, etc., to remove traces of HC1, had the followingproperties:

Viscosity at 100 F-- 445 Secs. Saybolt Universal Viscosity at 210 F 68Secs. Saybolt Universal Viscosity index 122 Pour 65 F.

Solid 60 F.

Example 6.-Metallic aluminum may be used as dechlorinating andpolymerlzing catalyst without the introduction of HC1 to initiate thereaction, as was exemplified above (Example 5). I n this event, however,higher temperatures must be used and a longer time of heating isrequired to give equivalent results. Thus, the dechlorination reactiondoes not begin below about 300 yF., and, if the dechlorination is to becompleted within 4-5 hours, the reaction temperature should be broughtto 400 to 450 F. At these higher temperatures, however, excellentresults are obtained, and the following oil, obtained in this mannerfrom a Wax-free chlorparamne containing 15.2% chlorine'with the use of1% of aluminum by weight, is typical:

Viscosity at 100 F-; 918 Secs. Saybolt Universal Viscosity at 130 F..-432 Secs. Saybolt Universal Viscosity at 210 F 109 Secs. SayboltUniversal Viscosity index 126 Pour 65 F. x Solid 60 F. i

Anhydrous aluminum chloride is in wide use as a dechlorinating agent,and also as a polymerization catalyst. It functions in the presentdechlorination-polymerization reaction to produce satisfactory highviscosity index oils, but we have found it less desirable than aluminumamalgam or metallic aluminum, whether or not the dechlorination reactionis initiated, in the latter case, with anhydrous HC1. As is well known,anhydrous aluminum chloride invariably forms an oil-insoluble sludgewhich contains a very considerable amount of hydrocarbon material heldin rather loose chemical combination. The formation of this sludgedecreases considerably the yield of oil that may be obtained in areaction such as that here discussed, for, as is well recognized, thehydrocarbons which may be obtained from the` sludge itself, for example,by decomposition with water, are of inferior quality and represent anutter loss except for use as a fuel or the like purpose.

In addition to loss in yield of high quality oil through the'formationof the typical aluminum chloride sludge, this catalyst is less desirablethan aluminum or aluminum amalgam by reason of its cost and because oi'the relatively large quantity required. Thus for dechlorination aloneViscosity at 100 F 97 Secs. Saybolt Universal Viscosity at 130"F 65Secs. Saybolt Universal Viscosity at 210 F--- 39 Secs. Saybolt UniversalViscosity index 87 Pour 55 F. Solid F.

It will be noted that there has been in this instance no appreciablepolymerization; to obtain appreciable polymerization, aluminum chlorideapproaching 10% in amount must be employed, with consequent increase inamount of sludge formed. In the above example, the yield of oil fromoriginal wax was 65 per cent by weight; in the preceding examples(Examples 1-6) the yields in each case were above 90%. From the above itwill be clear that although anhydrous aluminum chloride may be used asdechlorination and polymerization catalyst (especially the former), theuse of aluminum amalgam or of metallic aluminum, the latter either withor without the introduction of HC1 to initiate Ithe reaction, is muchpreferred.

The simultaneous use of both polymerizing (aluminum) andnon-polymerizing (clay) type catalysts hasbeen found of advantage, forin this manner the viscosity of the finished oil may be controlled. Inthe use of the two types of catalysts, aluminum or polymerizing type isallowed to function at relatively low temperatures, for example, 300 F.or thereabouts, until the reaction has proceeded sufficiently to produceoil ofthe desired viscosity; thereafter, the temperature is raised to ahigher point, for example 500 F. or thereabouts, and thenon-polymerizing type catalyst allowed to function until dechlorinationis complete. The following is an example of this method of operation.

Example 7.-Ch1orinated paramne containing 15.6% chlorine by weight, on awax-free basis, was heated with 10% by weight of the acidtreated clay ofthe montmorillonite type and 0.5 by weight of aluminum, for 1% hours at300 F. The temperature was then raised to 500 F. and held there forabout 30 minutes, by which time dechlorination was complete. ture wascooled and ltered free of clay and of aluminum. A light yellow oil witha green bloom was obtained; it had the following characteristics:

Viscosity at 100 F 423 Secs. Saybolt Universal Viscosity at 210 F.- 70Secs. Saybolt Universal Viscosity index 130 Pour 60 F. Solid F.

The reaction mixalone, until the reaction has proceeded suiiiclently toproduce an oil of the desiredviscosity; without removing any of thereaction products produced by the aluminum or aluminum amalgam reaction,other than the produced hydrogen chloride, we then add anon-polymerizing catalyst, continuing the heatinguntil dechlorination iscomplete. The results obtained in using such a sequence of steps aresimilar yto those of Example 7, above, with the advantage that controlof the character of the desired end product is in many casesfacilitated.

We have found, in general, that the viscosity of the finished oil can becontrolled by the correct selection of the chlorine content of thechlorinated paramne, the time of reaction and the temperature ofreaction. The following tabulation will make clear'how the practice ofour invention may be varied to produce oils, varying viscosity 20 andvarying viscosity index:

1n these experiments, aluminum amalgam was 35 used as dechlorinatingcatalyst.l

From the results above tabulated it appears that:

1. The viscosity and viscosity index of the synthetic oil are almostwholly dependent on the chlorine content of the chlorinated paramne. ehigher the chlorine content, the higher the viscosity and the lower theviscosity index.

2.. The reaction time and reaction temperature, within the limits shownabove, have relatively little effect onthe viscosity of the syntheticoils. These two factors control the degree of removal oi the chlorine.The temperature must be at least 250 F. for complete dechlorination in areasonable time. Also the higher the chlorine content, the longer thereaction time must be for the reaction to go to completion.

In blending the high viscosity index oils herein described with oils'oflow viscosity index,-for example, to improve in this respect the naph-55 thenic or mixed-base naturally occurring oils,-

it is to be pointed out that the viscosity index (as dened by Dean andDavis, supra) is not the arithmetic mean of the viscosity indices of theblended oils, but is in all cases considerably 50 higher. For example.the oil whose preparation was described above in Example 4 was blendedwith an equal volume of a naphthenic-type lubricating oil whoseviscosity index was 25, by the Dean and Davis method of calculation. Ihe

65 characteristics of the ons and of this 50-50 mend follows: y

Synthetic Naphthenii 50--50 v oil oil blend 70 Viscosity at 100 F 690687 643 Viscosity at 130 324 259 274 .viscosity as 210 F. ss so 7oviscosity index.. 124 25 94 It will be observed that the pour points ofseveral of the oils whose production is described above are higher thanis desirable for some lubricating purposes. The pour points of theseoils may be lowered by a dewaxing process, as mentioned above inconnection with Examples 2 and 4, or, if preferable, by adding smallamounts of a specially prepared pour point lowering compound, such as isdescribed, for example in U. S. Patent 1,815,022, issued July 14, 1931,to Garland H. B. Davis. Representative of the results obtained with theuse of the Davis compound, identied in the trade as Paraow, are thefollowing: f

While we have described in detail the character of our invention andgiven numerous illustrative examples of the preparation of synthetichydrocarbon oils of high Viscosity index, we have done so by way ofillustration and with the intention that no limitation should be imposedupon the invention thereby.

We claim:

1. The process of producing a liquid olenic hydrocarbon oil consistingof mono-oleilnes in major part and possessing a regulable viscosity anda viscosity'index of above 105, comprising passing chlorine gas into astraight chain parafine wax at a temperature above its melting point butnot above about 250 F., to produce chlorparaines containing not aboveabout 25% chlorine on a hydrocarbon-free basis, cooling the mixturecontaining unchlorinated wax hydrocarbons and produced chlorparaflinesto a temperature below the crystallizing temperature of theunchlorinated wax hydrocarbons, removing the crystallized unchlorinatedwax hydrocarbons, completely dechlorinating the chlorparaihnes andsimultaneously partially polymerizing the resulting straight chainolem'c hydrocarbons by heating the chlorparaines in the presence of twocatalysts, one of which is a dechlorinating and polymerizing catalystand.is selected from the group consisting of metallic aluminum and aluminumamalgam and the other of which is a dechlorinating andnon-polymerizng'catalyst and is selected from the group consisting offullers earth and montmorillonite clay, and separating the saidcatalysts from the produced entirely dechlorinated entirely olefinic andlargely mono-oleflnic high viscosity index hydrocarbon oil.

2. The process of producing a liquid oleflnic hydrocarbon oil consistingof mono-olenes in .f major part and possessing a regulable viscositypartial dechlorination of the chlorparaines and to cause polymerizationof the resulting oleflnic hydrocarbons, removing the said catalyst fromthe resulting mixture of chlorparaiiines and ole- `ilniox: hydrocarbons,and heating the said mixture of chlorparaiilnes and olenic hydrocarbonswith a second catalyst, selected from the group consisting of fullersearth and montmorillonite clay, to cause complete dechlorination of theremaining chlorparaillnes without the polymerization of the resultingolenic and largely mono-olenic high viscosity index hydrocarbons, andremoving the second catalyst from 'the produced entirely dechlorinatedentirely oleilnic hydrocarbon oil.

3. The process of producing a liquid oleiinic hydrocarbon oil consistingof mono-oleflnes in major part and possessing a viscosity index of above105, comprising passing chlorine gas into a straight chain parailine waxat a temperature above its meltingpoint but not above about 250 F., toproduce chlorparatnes containing not above about 25% chlorine on ahydrocarbonfree basis, cooling the mixture containing unchlorinated waxhydrocarbons and produced chlorparanes to a temperature below thecrystalllzingtemperature of the unchlorinated wax hydrocarbons, removingthe crystallized unchlorinated paraine wax hydrocarbons, adding metallicaluminum to the remaining liquid chlorparaillnes, passing dryhydrochloric acid gas into the admixture of chlorparaffines and-metallic aluminum at -a superatmospheric temperature until activedechlorination of the chlorparafnnes is initiated, discontinuing the,introduction oi, the hydrochloric acid while continuing the heating ofthe reaction mixture, whereby the chlorparafdnes are completelydechlorinated and the resulting oleflnes are simultaneously polymerized,and removing the metallic aluminum from the produced entirelydechlorinated en-l tirely oleiinic and largely mono-olenic highviscosity index hydrocarbon oil;

4. The process of producing a liquid olenic hydrocarbon oil of viscosityindex above 105 con sisting entirely of olenes and of mono-olenes inmajor part, comprising passing chlorine gas into a straight chainparalne wax at a temperature above its melting point but not above about250 F., to produce Chlor-paraffinescontaining not above about 25%chlorine on a hydrocarboniree basis, removing unchlorinated waxhydrocarbons from the produced chlorparailnes, completely dechlorinatingthe chlorparamnes and simultaneously polymerizing the resulting olenichydrocarbons by heating the chlorparafilnes in the presence of aluminumamalgam, and separating the said dechlorinating and polymerizingcatalyst from the produced entirely dechlorinated entirely oleflnic andlargely mono-oleflnic high viscosity index hydrocarbon oil.

5. 'I'he process of producing a liquid' olenic hydrocarbon oilconsisting of mono-olenes in major part and possessing a viscosity'index of above 105, comprising passing chlorine gas into a straightchain parafline wax at a temperature above its melting point but notabove about 250 F., to produce chlorparailines containing not aboveabout 25% chlorine on a hydrocarbonv.free basis, cooling the mixturecontaining unchlorinated wax hydrocarbons and' produced chlorparamnes toa temperature below the crystallizing temperature of the unchlorinatedwax hydrocarbons, removing the crystallized unchlorinated waxhydrocarbonazcompletely dechlorinating the chlorparafnes andsimultaneously polymerizing the resulting straight chain olefinichydrocarbons by heating the chlorparafnes in the presence of aluminumamalgam, and

,separating the said dechlorinating and polymerizing catalyst from theproduced entirely dechlorinated entirely oleilnic hydrocarbon oil.

6. The process of producing a liquid olenic hydrocarbon oil consistingof mono-oleiines in major part and possessing a regulable viscosity anda viscosity index of above 105, comprising passing chlorine gas into astraight chain parafilne wax at a temperature above its melting pointpoint but not above ab0ut250 F.,to produce chlorparaiines containing notabove about 25% chlorine on a hydrocarbon-free basis, cooling themixture containing unchlorinated wax hydrocarbons and producedchlorparaiiines to a temperature below the crystallizing temperature ofthe unchlorinated wax hydrocarbons, removing the crystallizedunchlorinated wax hydrocarbons, completely dechlorinating thechlorparaiilnes and simultaneously partially polymerizing the resultingstraight chain olefinichydrocarbons by heating the chlorparaiilnes inthe presence of two catalysts, one of which is a dechlorinating andpolymerizing catalyst and is aluminum amalgam and the other of which isa dechlorinating and nonpolymerizing catalyst and is selected fromv thegroup consisting of fullers earth and montmorillonite clay, andseparating 'the said catalysts from the produced entirely dechlorinatedentire- 7. 'Ilie process of producing a liquid oleiinic hydrocarbon oilconsisting .of mono-oleiines in major part and possessing a regulableviscosity and aviscosity index of above 105, comprising passing chlorinegas into a, straight chain paraffine waxat a temperature above itsmelting point but not above about 250 F., to produce chlorparaiilnescontaining not above about 25% chiorine on a hydrocarbon-free basis,cooling the mixture containing unchlorinated wax hydrocarbons andproduced chlorparaillnes to a temperature below the crystallizingtemperature of the unchlorinated wax hydrocarbons, removing thecrystallized unchlorinated wax hydrocarbons, heating the chlorparaiiineswith aluminum amal- Ygam to cause only partial dechlorination of thechlorparaiilnes and to cause polymerization of the resulting oleinichydrocarbons, removing the said catalyst from the resulting mixture ofchlorparamnes and oleflnic hydrocarbons, and heating the said mixture ofchlorparamnes and oleiinic hydrocarbons with a second catalyst, selectedfrom the group consisting of fullers earth and montmorillonite clay, tocause complete dechlorination of the remaining chlorparaiilnes withoutthe polymerization of the resulting oleilnic hydrocarbons, and removingthe second catalyst from the produced entirely dechlorlnated entirelyoleiinic and largely mono-oleinic high viscosity index hydrocarbon oil.

8. A process of producing a high viscosity index i the other of which isa dechlorinating and non- Y polymerizing catalyst and is selected fromthe ,75

aosaaoc group consisting of fuilers earth and montmorillonite clay, atelevated temperatures, and separating the catalysts from thedechlorinated hydrocarbon oil.

9. A process of producing a high viscosity index lubricating oil whichcomprises chlorinating straight chain paraiine hydrocarbons to achlorine content of between 10 and 25% on a hydrocarbon-free basis,removing unchlorinated hydrocarbons, heating the chlorparafnes with acatalyst selected from the group consisting of metallic aluminum andaluminum amalgam to cause only partial dechlorination of thechlorparaiilnes and to cause polymerization of the resultingdechlorinated chlorparaflines, removing the said catalyst from theresulting mixture of vchlorparaines and hydrocarbon polymers, heatingthe said mixture of chlorparafflnes and hydro.-

carbon polymers with a second catalyst, selected from the groupconsisting of fuilers earth and montmorillonite clay to cause completedechlorination of the remaining chlorparanes without the polymerizationof the resulting dechlorinated hydrocarbons, and removing the secondcatalyst from the dechlorinated hydrocarbon oil.

10. A process of producing a high vviscosity index lubricating oil whichcomprises chlorinating straight chain paraine hydrocarbons to a chlorinecontent of between 10 and 25% on a hydrocarbon-free basis, removingunchlorinated hydrocarbons, adding metallic aluminum to the liquidchlorparamnes, passing dry hydrochloric acid gas into the'admixture ofchlorparafiines and metallic aluminum at a super-atmospheric temperatureuntil active dechlorination of the chlorparalnes is initiated,discontinuing the introduction of -the hydrochloric acid whilecontinuing the heating of the reaction mixture to eiect a completedechiorination of the chlorparafiines, and removing the metallicaluminum from the dechlorinated hydrocarbon oil.

11. A process. of producing a, high viscosity index lubrlcating oilwhich comprises chlorinating straight chain paraiiine hydrocarbons to achlorine content of between 10 and 25% on a hydrocarbon-free basis,removing unchlorinated hydrocarbons, completely dechlorinating thechlorparafdnes and simultaneously polymerizing the resultinghydrocarbons by heating the chlorparaiilnes in the presence of aluminumamalgam, and separating the aluminum amalgam from the dechlorinatedhydrocarbon oil.

ELMSLIE W. GARDINER. JOHN W. GREENE. VR'I'I-IIUR L. LYMAN.

